Overhead Projector .

- ٧٦ -
Wohler
1828

- ٧٧ -
 Functional Groups

sp3 – OH

Functional Group

O
C H

- ٧٨ -
 O
[O]
O CH 3C-OH ( )
CH 3C H
[H]
CH3CH2OH ( )

[O]
O CH3CH2COOH ( )
CH3 CH2C H
[H]
CH3CH2CH2OH ( )

[O]
O CH3CH2CH2COOH ( )
CH3CH2CH2C H
[H]
CH3CH2CH2CH2OH ( )

( -CHO )

- ٧٩ -
 H2C C H2 C=C

H C C H C C
X
Br
C
CH 3I ,
( X = I, Br, Cl , F )

CH 3CH 2OH C OH

CH 3 O CH3 C O C

O O
CH3 C H C H
O O

CH3 C CH3 C C C

O O
H C OH C OH
O O
C Y
CH3 C OCH 3 ( Y = Cl ,OR, NR 2 ,...)
CH3
C N
CH3NH2 , CH3NH

CH3CN C C N

- ٨٠ -
 NO2 O
CH3NO2 , C N O-

CH 3SH C SH

hemolytic
heterolytic
X

.
C . .X C. + X " "

_
C . .X C + + .. X

carbonium ion
" "

_
C . .X C .. + X +

carbanion

- ٨١ -
 X

Nu- Electrophiles E+
Nucleophiles

H+ , Br+ , NO2+ , BF3 , AlCl3

. ._. . . _. . ._ . ._ ..
HO . , RO . , RS .. , CN .. , H2O .. , R2N ..
.. .. ..

- ٨٢ -
 substitution

CH 3CH 2OH + HBr CH3CH 2Br + H2O

addition

CH 2 CH2 + Br2 CH2BrCH 2Br

elimination

CH3CH2Br + NaOH CH2 CH2 + H2O + NaBr

sp2 sp3
sp

- ٨٣ -
 sp3
CH4

1s2 2s2 2px1 2py1

Linus Pauling
2s
2pz

- ٨٤ -
 sp2
2s 2py 2px sp2
s p

sp2
sp2 2px o

sp
2p 2s sp2 sp3
sp
2p

- ٨٥ -
 H-C C-H
o

2pz 2py

s
p s
sp3 s
C-C sp3

- ٨٦ -
d p

- ٨٧ -
H (C)

saturated
Ethane CH3-CH3 alkanes –

unsaturated

– alkenes
C=C

- ٨٨ -
– alkynes
C C

Aromatic Hydrocarbons
C10H8 C6H12

Alkanes

- ٨٩ -
n CnH2n+2
n = n
n>20

-ane

-ane

N
1 methane CH4
2 ethane CH3CH3
3 propane CH3CH2CH3
4 butane CH3CH2CH2CH3
5 Pentane CH3(CH2)3CH3
6 hexane CH3(CH2)4CH3
7 heptane CH3(CH2)5CH3
8 octane CH3(CH2)6CH3
9 nonane CH3(CH2)7CH3
10 decane CH3(CH2)8CH3

- ٩٠ -
CH2
Methylene

Butane C4H8

Pentane C5H12

Alkyl Group R-
R-
methyl CH3-
Ethyl CH3CH2-

- ٩١ -
 Methyl CH3 Methane CH4
Ethyl CH3CH2- Ethane CH3CH3

N-Propyl CH3CH2CH2- Propane CH3CH2CH3

Isopropyl CH3-CH-CH3 CH3CH2CH2CH3
n-Butyl CH3CH2CH2CH2-
sec- Butyl CH3CHCH2CH3 n-Butane
Isobutyl CH3 CH3
CH3 CH CH2 _ CH3 CH CH3

CH3
Tert-butyl CH3 C Isobutane
CH3

Cycloalkanes

- ٩٢ -
 I UPAC

IUPAC International Union of Pure and Applied

Chemistry

ane
yl

penta tetra tri di

- ٩٣ -
ane yl

- ٩٤ -
 F: Fluoro NO2 Nitro

Cl Chloro NH2 Amino

Br Bromo CN Cyano

I Iodo

iso-
neo-
tri di sec- tert-

nonpolar
C5 C4 C1
C17

- ٩٥ -
 combustion
–

CH 4 + 2O 2 CO 2 (g) + 2H2O +
(g)

Halogenation
Br2 Cl2

- ٩٦ -
- ٩٧ -
Refining

Grignard reagents

- ٩٨ -
Lithium dialkyl copper (
R2CuLi)

- ٩٩ -
 alkenes
C=C –
CnH2n olefins
C2H4 CnH2n-2

H 120 H
C = C
H H

–ylene alkane –ane

- ١٠٠ -
 Alkene Alkane

Ethylene CH 2=CH 2 Ethane CH3CH3

Propylene CH3-CH =CH2
Propane CH 3CH 2CH 3
Butylene CH3CH2CH=CH2

B-Butylene CH3CH=CHCH3 n-Butane CH 3CH 2CH 2CH 3

Isobutylene CH3 CH = CH2 Isobutane CH3 CH CH3

CH3 CH3

CH2=CH2
( Vinyl group ) –CH=CH2

CH2 = CH

Vinyl Cyclohexane

( allyl group) CH3CH=CH2

IUPAC

- ١٠١ -
 IUPAC

–ene –ane

5 4 3 2 1
CH3CH-CH = CH-CH3

CH3
4- Methyl - 2- Pentene

CH2 = CH2 CH 3 -CH = CH 2 CH3CH2CH = CH2

Ethene Propene 1-Butene
CH2-CH = CH2

Cl
3-Chloro -l- Propene
2-Ethyl-1-Butene

- ١٠٢ -
 6
3
5 1 4 2
4 2
3 5 1
6
Cyclohexene 3-Methylcyclohexene
(1-Cyclohexene ) (6-Methylcyclohexene )

–ene tetra tri di

5 4 3 2 5
CH2 = CH-CH2-C-CH2CH 3 1 4
2 4 6
1 CH2
1 3 5 7 2 3
2-Ethyl,1,4-Pentadiene
1,3,6-Heptatriene 1,3-Cyclopentadiene

2-butane 1-butene
2-
butene

H CH3 CH3 CH3

C C C C
CH3 H H H
Cis-2-butene
trans-2-butene

- ١٠٣ -
 – cis
trans
trans-2- cis-2-butene
butene

- ١٠٤ -
 H+
H3PO4 H2SO4

H H H H
+
H ,
H C C H C C + H2O
OH H H H

( ) ( )

KOH ( I , Br, Cl =X ) HX

KOH / + -
CH2 CH2 CH2 = CH2 +K +CI +H2O

H Cl

- ١٠٥ -
 H2SO4

CH2 = CH2 + H2SO4 CH2 CH2

H OSO3H

Polymerization
– –
polymers

Naphtha fraction

- ١٠٦ -
Cr2O3+Al2O3)

( X = Cl ,Br, I ) HX

C C + HX C C
H X

CH2=CH2 + HCI CH3 CH2 CI

( )

Markovnikov's Rule

Hydration
H+

- ١٠٧ -
 Hydrogenation
Catalysts Pd Ni Pt

Pt or Ni
CH2 = CH2 + H2 CH3 CH3

Halogenations

C C + X2 / CCI4 C C

(X = CI , Br) X X

- ١٠٨ -
 –

Alkynes
C C –
C2H2 CnH2n-2
sp

CaO
CaS2

2500 oC
3C + CaO CaC2 + CO

CaC2 + 2H2O C2H2 + Ca(OH)2

IUPAC

–
–ene yne

HC CH CH3C CH CH3CH2C CH
Acetylene Methyl acetylene Ethyl acetylene
Ethyne Propyne 1- Butyne

- ١٠٩ -
 : IUPAC

–yne
alkene

–yne

- ١١٠ -
 C17 C16 C4 C4 C2

Dehydrohalgenation

- liq NH3
HC C Na+ + CH3Br HC C CH3 + NaBr

- liq NH3
HC C Na+ + CH3CH2I HC C CH2CH3 + NaI

- ١١١ -
CH4 + O2 2HC CH + 2CO + 10H2

- ١١٢ -
 R R
Pd or Ni H2\Ni
R C C R + H2 C=C RCH2CH2R
H H

Linders catalyst Pd + Pb(OAc)4 Ni-B2

Pd/CaCO3)

- ١١٣ -
 mercuric sulfate

- ١١٤ -
 O O
-
1)KMnO4 /OH
- R C C R
2)H2O / OH
O O
-
1)KMnO4 /OH
R C C R R C OH + R C OH
2) 100C / H +

1)O3
RCOOH + RCOOH
2)H2O /Zn Or H2O2

Aromatic Compounds

Aromatic)
OCH3
C6 H 5 COOCH3 COOH
C6H5

- ١١٥ -
 C6H6

sp2
C=C (A –
A) C-C A)
Kekule

I II

I Hybrid II I
II
Delocalized

- ١١٦ -
 Huckels rule
n = 0 ,1, 2,3 4n+2)

(4x1+2) = 6

Benzen Naphthalene Anthracene

n =1 n =2 n =3

..
N N
..
Pyrole
Phenanthrene Pyridine
n =1
n=3 n =1
4(1)+2=6 es
4(3)+2=14 es 4(1)+2=6 es
- +
+

n=0 n =1 n =1
4(0)+2=2 es 4(1)+2=6 es 4(1)+2=6 es

- ١١٧ -
 - +

º
º

Br I CH2CH3

Bromobenzene Iodobenzene Ethylbenzene

NO2

Nitrobenzene

- ١١٨ -
 CH 3 CH=CH2 _
CH3_ CH CH3
CHO

Toluene Styrene Cumene Benzaldehyde

OH COOH O
NH2
C _ CH3

Phenol Benzoic acid Acetopnenone Aniline

OCH3
SO3H

Benzenesulfonic acid Anisole

phenyl

2-Phenylbutane 2-Phenylethanol

Benzyl
Benzal
Benzo

- ١١٩ -
 CH2Cl CHCl2 CCl3

Benzylchloride Benzaldichloride Benzotrichloride

ortho O
meta m
para p
Benzene

F
CI CH2CH3
CI

CI
I
O-dichlorobenzene m-chloroethylbenzene
p-fluoroiodobenzene
CH 3 COOH OH
CI

NO 2 Br
m-nitrotoluene m-bromobenzoic acid o-chlorophenol

CH3-

CH 3
CH3 CH3
CH3

CH3
CH 3
- ١٢٠ -
 o-xylene m-xylene p-xylene

CI
2
CI NO2
CI 1 1
3 6 2
6 4 5 3
5 CI
F 4
1,2,3-trichlorobenzene
3-chloro-5-fluronitrobenzene
‫وليس‬
( ١ ‫) ﳎموعة النيترو ﳚب أن تقع على ذرة الكربون رقم‬
(1,2,6-trichlorobenzene)

OH CH3
Br 1
Br NO2 NO2
6 2
5 3
4
Br NO2
2,4,6-tribromophenol 2,4,6-trinitrotoluene (TNT)
( ١ ‫)ﳎموعة الفينول ﳚب أن تقع على ذرة الكربون رقم‬ (١ ‫) ﳎموعة اﳌيثيل ﳚب أن تقع على ذرة الكربون رقم‬

- ١٢١ -
 ‫أ ‪ -‬تفاعﻼت اﳍلجنة ‪: Halogenation‬‬

‫‪- ١٢٢ -‬‬

- ١٢٣ -
Ethylbenzene
Cyclohexane
CH2CH3 CH2CH3
Ni,Pt or Pd
+ 3H2

Ethylbenzene Ethylcyclohexane

Alkylation –

- ١٢٤ -
 Acylation ( ‫ أسيلة ) فريدل – كرافت‬- ‫د‬

Halogenation ‫ اﳍلجنة‬- ‫ه ـ‬

Nitroation ‫ النيترة‬- ‫و‬

Sulfonation ‫ السلفنه‬- ‫ز‬

- ١٢٥ -
 Anisole
nitroanizole

CH3C+ =O R+
H+ Br+ NO2+

- ١٢٦ -
 -NH2(-NHR,-NR2) ,-OH >-OR,-NHCOCH3 > -C6H5 ,-R

R
–
-F,-Cl, - Br )

-NO2, -N+(R)3,-C=N,COOH( -COOR ),-SO3H,-CHO,-COR

NO2 NO2
HNO3 Br2,Fe
H2SO4
Br
m-bromonitobenzene
Br Br Br
NO2
Br2,Fe HNO3
+
H2SO4

NO2
o-bromonitro p-bromonitro
benzene (38%) benzene (62%)

- ١٢٧ -
- ١٢٨ -
R R - X
X

Cl, Br, F, …

(F, Br, Cl, ..) X

- ١٢٩ -
 Alkyl
IUPAC

CH3Cl CH3CH2CH2Br
1 halides
(Methyl chloride) (n – propyl bromide)
Chloromethane 1 - Bromopropane

2ºhalides

3º halides

- ١٣٠ -
 CCl4 CHCl3 CH2Cl2
(Carbontetrachloride) (Chloroform) (Methylene chloride)
Tetrachloromethane Trichloromethane Dichloromethane

CHBr3 CHI3
(Bromoform) (Iodoform)

- ١٣١ -
 .

- ١٣٢ -
 .
HX
PCl5 , PCl3 , PBr3 SOCl2

HCl
CH3(CH2)5 CH2OH CH3(CH2)5 CH2 +H2O
ZnCl2 / 150
Cl

- ١٣٣ -
 Nucleophilic substitution reactions

+ - –
R3 C R3C-Nu +

O
- - - -
SR , SH , CH3NH2 , NH3 , - O - C - R , OR ,OH

.. - -
N (CH3) 3 , HN (CH3)2 , CN ,R - C = C

- ١٣٤ -
 Elemination reactions E

-4

Grignard formation

- ١٣٥ -
 D.D.T.

–[ CF2–CF2]nTeflon
– [H2–CCl2]n –
–[ CH2 – CHCl2-]n – PVC
CCl3F CCl2F2 CF3CHClBr HCX3haloform

Antifungus Antibiotics

- ١٣٦ -
 ‫‪OH‬‬
‫‪R‬‬ ‫‪R‬‬ ‫‪ROH‬‬

‫‪sp2‬‬ ‫‪sp3‬‬

‫كحول ثالثي‪Tertiary 3O‬‬ ‫كحول ثانوي‪Secondary 2O‬‬ ‫كحول أوﱄ‪Primary 1O‬‬

‫‪H‬‬ ‫‪R‬‬ ‫‪H‬‬
‫‪R‬‬ ‫‪C‬‬ ‫‪OH‬‬ ‫‪R‬‬ ‫‪C‬‬ ‫‪OH‬‬ ‫‪R‬‬ ‫‪C‬‬ ‫‪OH‬‬
‫‪R‬‬ ‫‪R‬‬ ‫‪H‬‬
‫ذرة الكربون الﱵ ﲢمل ﳎموعة ‪ -OH‬ﻻ‬ ‫ذرة الكربون الﱵ ﲢمل ﳎموعة‬ ‫ذرة الكربون الﱵ ﲢمل ﳎموعة‬
‫ﲢتوي على ذرات هيدروجﲔ ولكن ﲢتوي‬ ‫‪ -OH‬ﲢتوي على ذرﰐ هيدروجﲔ ‪ -OH‬ﲢتوي على ذرة هيدروجﲔ‬
‫على ثﻼث ﳎموعات ألكيل‪.‬‬ ‫وﳎموعﱵ ألكيل‪.‬‬ ‫وﳎموعة ألكيل ‪.R‬‬

‫‪- ١٣٧ -‬‬

IUPAC

CH3 OH CH3CH2OH CH2=CH-CH2OH

Methyl alcohol Ethyl alcohol Allyl alcohol

OH
ol e

- ١٣٨ -
-OH

- ١٣٩ -
-ol tetra , tri ,di

- ١٤٠ -
 R Ar
Ar
O O
O O
H H
R H H

.
Ethanol Propane
°

- ١٤١ -
 :

Ethanol Methanol

water gas

Water gas
o
300 atm 300

Natural gas

o
900

- ١٤٢ -
 Synthesis

: Ethyl hydrogen sulphate

Phosphoric acid on silica

o
70 atm

- ١٤٣ -
 Oxidation
1

- ١٤٤ -
- ١٤٥ -
 H+

- ١٤٦ -
 C=O

O
R(Ar)-C-H

Ar R

O
R C R

R , R

IUPAC

ic acid
aldehyde

- ١٤٧ -
 O
Formic acid
H C H
Formaldehyde
O

CH 3 C H Acetic acid

Acetaldehyde

(C C C C O)

ketone

- ١٤٨ -
 O
O
CH3 C CH3
CH3 C CH( CH3)2
Dimethyl ketone
Methyl isopropyl ketone ( acetone )

Phenyl phenone
-oic acid -ic acid

O O

C CH3 C
Acetophenone Benzophenone

al e
–

CH3 O
O
CH3 CH CH2 C H
CH3 C H
Ethanol 3-Methyl butanal

- ١٤٩ -
 O

C H
O

C H CH 3

Benzaldehyde p-tolualdehyde

e al one

IUPAC

+ -
C=O

- ١٥٠ -
 O
C O H H

37 Formalin

56

- ١٥١ -
- ١٥٢ -
 o
500 2-propanol

.(Cyanohydrine ) HCN

- ١٥٣ -
 G-NH2

NH C NH2
NH Ar OH H=G

- ١٥٤ -
 Reduction

NaBH4

Oxidation

O O
(O)
R C H R C OH

- ١٥٥ -
COOH)
-OH C=O

Formic acid Formic

HCOOH

Acetic acid Acetum

CH3COOH

Butyric acid Butyrum

CH3(CH2)2COOH

- ١٥٦ -
 O
C C C C C C OH
5 4 3 2 1

IUPAC
e oic acid

- ١٥٧ -
 O
Br
CH 3 C OH
CH3 CH COOH
Ethanoic acid
(Acetic acid) 2-Bromopropanoic acid

COOH
CH3

CH3 C CHCOOH
3-Methyl-2-butenoic acid
Cyclohexane
Carboxylic acid

CH3

COOH OH
COOH

COOH

Benzoic acid Salicylic acid P-Toluic acid

- ١٥٨ -
 Fatty acids
26 12

- ١٥٩ -
.(Ar)R-CN

- ١٦٠ -
- ١٦١ -
- ١٦٢ -
 O O
CH3OCH 2CH2C H CH 3C N(CH 3)2

b) - CH 3CH 2I + NaSH CH3CH2SH + NaI

c) - CH2 CH CH 3 + HCl CH3CHCH 3

Cl

- ١٦٣ -
 IUPAC

CH3

C2H5
CH3
CH C CH
CH3

CH3 C = C CH3
CH3 Br

2-chloro-3-methyl-2-pentene 2 , 3 - d i m e t h y l b u t a n e
2,2-Dibromo-3-hexyne

- ١٦٤ -
 IUPAC

Br
CH3CH_ CH _ CH3
Br CH3
NO2
_ _
CH 3 CH2 CH=CH 2
Cl

3 2 1

Br
CH3 Cl CH3
CH3 C CH3
Cl

CH3 CH3
Br2 HCl
CH3CHCH3 hv CH3CHOH ZnCl
2
KOH NH2CH3
CH 3CH_ CH3 CH3CH2CH2Cl
EtOH /
Br

-
OH
CH 3CHBrCH 3 ethanol
-
OH
CH 3CHBrCH 3 H2O
H2O
(CH 3)3CBr

- ١٦٥ -
3 2 1

2,4-Dimethyl-2-Octanol

- ١٦٦ -
O
Cl O

CH 3CH 2C H

(CH 3)2CHCCH(CH 3)2

Benzaldehyde
Benzylphenyl ketone
3-Pentanone

- ١٦٧ -
 CO 2H
OH
O

CH 3 CH 2 C OCH 3

NH2

O O
O
C O C CH 3
CH 3 CH 2 C Cl

2,3-dibromopentanoic acid
Methyl formamide
Potassium formate
Benzoic formic anhydride

KMnO 4
CH 3 CH 2H5

O +
H
CH3 C OH
- ١٦٨ -
 CH3NH2
CH3OH
F-
ZnCl2

- ١٦٩ -
 2,2- Dimethyl Propane
3-Ethyl-1-Methyl cyclohexane
3-Methyl -1- butyne
2- Bromo -3-Methyl -2- butene

CH3 - CH -CH -CH3

CH3 CH3
CH3 C C CH2CH 3
Cl CH3
Br
CH3 C C CH2CH 3
Br

CH4 +2O 2 CO2 + 2H2O +

+
H ,
CH3 CH2 OH CH2 = CH 2 + H2O
CCI4
CH3 - CH = CH - CH 3 + Br2 CH2CH - CH CH 3
Br Br

- ١٧٠ -
 2-Bromo-3-methyl butane
1-Bromo-2-Nitro cyclohexane
1-chloro-1-butene

1
2
3

CH3 CH3
HCl
CH3CHOH ZnCl CH3CHCl + H2O
2

CH3 CH3
Br2
CH3CHCH3 hv CH3 C CH3
Br
NH2CH3
CH3CH2CH2Cl CH3CH2CH2NHCH 3
KOH
CH3CH_ CH3 CH3CH=CH 2 + HBr
EtOH /
Br

- ١٧١ -
 3o 1,1-Diethyl propanol
2o 1-Bromo-2-propanol

CH3
CH3-CH2-CH2-CH2-C-CH2-CH-CH3
CH3 OH

Propanol
Methyl propyl ketone
2-Chlorocyclohexanone

O CHO

CH3 CH2 CH2 C-H

O
CH3 CH2 CH2 C-CH3

- ١٧٢ -
 4-Amino-2-hydroxy benzoic acid
Methyl propanoate
Acetic benzoic anhydride
Propanoyl chloride

O CH 3-CH2-CH-CH-COOH
H-C-NHCH 3 Br Br

O O O _
+
-C-O-C-H H-C-O K

CH3
H+

O
HOOC COOH
CH3-C-O C 2H5

- ١٧٣ -
- ١٧٤ -
1. G.D Christian: Analytical Chemistry, 5th edition, John Wiley &Sons, Inc, International edition,
1994.
2. G.H. Jeffrey, J. Bassett, J. Mendham, R.C. Denney: Vogel's Textbook of Quantitative
Chemical Analysis, 5th edition, Longman Scientific & Technical, 1989.
3. D.A. Skoog, D.M. West and F.J. Holler, Analytical Chemistry – An Introduction, Saunders
College Publishing 6th edition, International edition, 1994
4. Fessenden, Ralph J.and Fessenden, Joan S. Organic Chemistry ,2nd ed, PWS, Boston 1982.
5. F.A. Carey. Organic Chemistry, McGraw Hill, 2001.